Production of vinyl chloride



' Patented Aug. ,31, 1943.

PRODUCTION OF YINYL CHLORIDE- Ralph W. Dornte, Alplaus, N. Y, assignor to General Electric Company,

York

a corporation of New No Drawing. Application February 16, 1942,

Serial No. 431,132 I 3 Claims.

The present invention relates to an improved process for the production of vinyl chloride from generator gas produced by subjecting a hydrocarbon oil to the action of electric are or arcs.

It has been known that vinyl chloride may be prepared by saturating acetylene and hydrogen chloride with mercury and then contacting the reactant gases with a catalyst of activated carhon. Diiliculty has been encountered, however, in the process due to the fact that gas obtained from the electric-arc process contains certain compounds which act as catalytic poisons. It has been proposed to remove these poisonous elements by refrigerating the generator gas at a temperature of the order of --80 :0. but this has proven not-entirely satisfactory. Moreover, While the usual catalyst employed in reacting acetylene with hydrogen chloride to form vinyl chloride, for example mercuric chloride supported on a porous body, functions satisfactorily with pure acetylene and hydrogen chloride, such catalysts have serious limitations when used with agaseous mixture obtained by subjecting a'hydrocar-b'on oil to' the action of an electric are or arcs. For convenience such a mixture will be termed herein as genera-v tor gas. The generator gas contains in addition to theacetylene a high percentage, for example about 50-60% hydrogen. The instability of mercuricchloride in the presence of hydrogen probably is, one cause of the difficulties which are experienced with suchcatalyst. j I

I have discovered that the foregoing difficulties are obviated by first treating the generator gas to remove the catalytic poisons and then contacting the reactants with-a specially prepared catalyst. My invention, thereiore,includesnot '-only an improved process for preparing-the vinyl chloride but also an improved catalyst for the reaction and a method of preparing such cata-- I to lyst.

In order to lustrate my invention the following detailed description of the process for producsisting of acetylenics, olefines, saturated hydrocarbons, hydrogen sulfide and other sulfur coma pounds. r

The generator gas first is subjected to a purification process toremove components which are active poisons for the catalyst. Although it is not definitely known which components of the gas 1 mixture are the poisonous elementsfor the catalyst used in the process, sulfur compound havebeen identified among the poisonous elements. However, it is known that it is extremely important to remove these poisonous components before the reactants are allowed to come in contact with the catalyst.

In order to purify the gaseous product it is scrubbed with a dilute alkaline solution, for example a sodium hydroxide solution or its equivalent, and then dried by conducting it over a deliquescent material such as solid sodium hydroxide, calcium chloride, etc. Finally, the gaseous mixture is passed over an activated adsorbent material which is capable of being regenerated, such as activated alumina, silica gel and the like.

Instead of refrigerating the gas at -78 C., as heretofore proposed which involves potential hazards, and also apparentlydoes not remove entirely all of the poisonous elements due to limitations arising from the vapor pressure of the condensible poisons, I have found that when" the gas is passed at 20 C. over any suitable activated carbon such as industrial activated carbon, co-

'coanut charcoal, etc., prior to contact with the catalyst for the reaction,t hese poisonous elements are completely removed. Thus, for example, I have found that one volume of activated ing vinyl chloride including the process of preparingthe improved catalyst for'the reaction is given. 1

The gases employed in, the process may-be generated for example by the operation of electric.

arcs between particles of carbon in oil-as described and claimed, for example, in the copending application of Chauncey G. Suits, Serial No.

380,640, filedFebruary 26,1941, and assigned to the same assignee as'the present invention. Such a gas contains a relatively high percentage, ap-

proximately -30% by volume of acetylene and -60% by volume of hydrogen, the balance con carbon (6-8 mesh) removes all the condensible poisons from 490 volumes of generator gas. The f adsorptive capacity of the activated carbon may be" regenerated by heating under vacuum at a temperature of 200-400 C., any acetylene which may have been adsorbed, being desorbed and returned, if desired. to the gas generator.

The gas so purified is now ready for reaction with anhydrous hydrogen chloride. 'In'order to effect this reaction a specially prepared catalyst is employed. An example of the, preparation of the catalyst follows:

Twelve (12) liters of 618 mesh of an activated carbon is dried by heating under a. vacuum (1-10 I mm.) at 300-400" C. The average time for carrying out this dryingoperation is of the order 01.10 hours. The activated carbon then is saturated with mercury at 200 C.- by distilling ithe mercury through the catalyst tubecontaining I l l with a gas rate of 21 liters per minute.

the carbon andwnile under yacuum. The activated carbon then is treated at 135-200 C. for an average time of about 4 hours with a stream of anhydrous hydrogen chloride which causes the formation in situ upon the activated carbon particles of mercurous and mercuric chlorides.

99%, conversion to vinyl chloride is obtainedwhile a 96% conversion to vinyl chloride results This is a marked improvement over prior art processes since the present invention provides a 96 to 99% conversion with a gas rate of from two to four times that known orindicated in the prior art.

comprises scrubbing said generator gas, drying the gas, conducting the gas over an activated car- 19011 to remove condensible catalytic poisons, mixing the purified gas with anhydrous hydrogen chloride, passing this gas mixture over heated metallicmercury and finally over a catalyst comprising an activated carbon saturated-with mercury and containing mercurous and mercuric chlorides formed in situ on the surface of the activated The efficiency of the process, and the catalyst in particular, is indicated by the almost negligible ample, with a flow of from 9 to 10 liters per 'minute of generatorgas only 0.1% to 0.2% of acetylene is found in the exhaust gas and an excess of about 200 cubic centimeters of hydrogen per minute. The high activity of the catalyst is indicated by the temperature rise at the inlet to 200 C. in spite of the air cooling on this section of the catalyst while the remainder of the catalyst is held at 130 to 150 C. by electric heating. Similar results are obtained with a gas rate of 18 liters per minute which gives only 0.1% to 0.3% acetylene in the exhaust from the catalyst.

What I claim as new and desire to secure by Letters Patent of the United'states is:

l. The process of producing vinyl chlorideirom generator gas produced by subjecting a hydrocarbonoil to the action of electric arcs, which carbon.

. 2. The process of producing vinyl chloride from generator gas produced by subjecting a hydrocarbon oil to'the action of electric arcs, which comprises scrubbing said generator gas with 20% NaOH solution, drying the scrubbed gas by first passing it over solid NaOH and then over activated alumina, conducting the gas so scrubbed and dried over an activated carbon to remove condensible catalytic poisons, mixing the purified gas with anhydrous hydrogen chloride, passing this gas n iixture over heated metallic mercury and finally over a catalyst comprising an activated carbon saturated with mercury and containing mercurous and mercuric chlorides formed in situ on the surface of the activated 3. The process of preparing a catalyst for use in producing vinyl chloride from hydrogen chloride and generator gas produced by subjecting .a hydrocarbon oil to the action of electric arcs,-

which comprises-heating an activated carbon under vacuum at elevated'temperature, distilling 4 hydrogen chloride. through the carbon-mercury mixture to form in situ mercurous and mercuric chlorides on the surfaces of the carbon particles.

RALPH W. DORNTE. 

